CN109134274A - A method of separation ethylenediamine and n-ethylethylenediamine mixed solution - Google Patents
A method of separation ethylenediamine and n-ethylethylenediamine mixed solution Download PDFInfo
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- CN109134274A CN109134274A CN201811194713.0A CN201811194713A CN109134274A CN 109134274 A CN109134274 A CN 109134274A CN 201811194713 A CN201811194713 A CN 201811194713A CN 109134274 A CN109134274 A CN 109134274A
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- ethylethylenediamine
- ethylenediamine
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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Abstract
The present invention relates to a kind of methods for separating ethylenediamine and n-ethylethylenediamine mixed solution, belong to Separation of Organic Compounds technical field, the mixed solution for mass fraction less than 60% is specifically included, by the operation order separation ethylenediamine and n-ethylethylenediamine crystallized deeply after first partially crystallizable；It is equal to or more than 60% mixed solution for mass fraction, by the operation order separation n-ethylethylenediamine and ethylenediamine of partially crystallizable after first deep crystallization；Last remaining mixed solution recycled；Ethylenediamine and the yield of n-ethylethylenediamine can reach 50% or more after the chilled Crystallization Separation of mixed solution in the present invention, and purity can reach 98% or more；Operation of the present invention is simple, high-efficient, energy consumption is small, at low cost.
Description
Technical field
The present invention relates to a kind of methods for separating ethylenediamine and n-ethylethylenediamine mixed solution, belong to organic compound point
From technical field.
Background technique
The main method of industrial synthesis n-ethylethylenediamine is alkyl halide ammonolysis process.N- ethyl second two is produced in this way
Amine, ethylenediamine is excessive in mix products after the reaction was completed.When ethylenediamine content is higher, ethylenediamine and n-ethylethylenediamine
Relative volatility extracts close to 1(chemical industry and engineering, the 5th phase of volume 27 in 2010, n-ethylethylenediamine and ethylenediamine system
Distillation solvent is taken to select, Huang Xueli, Li Yongxia, Ou Chuanqi etc.), therefore ethylenediamine and the mixed solution of n-ethylethylenediamine belong to
Difficult separation mixture, their separation are relatively difficult.The separation of ethylenediamine reported in the literature and n-ethylethylenediamine mixed solution
For azeotropic distillation, (petrochemical industry, the 2nd phase of volume 36 in 2007, ethylenediamine and n-ethylethylenediamine extract the main method used
Take the selection of distillation solvent, Cui Xianbao, Huang Yue, Guo Yongxin etc.), n-ethylethylenediamine, n-ethylethylenediamine are separated with this method
Yield is 70.7%.
In patent CN102816071A, Cui Zixiang etc. is obtained after preparation n-ethylethylenediamine using the method for extracting rectifying
To mix products in separate n-ethylethylenediamine, the extractant selected in patent is glycerine.Mixed solution is through extracting rectifying
N-ethylethylenediamine is obtained afterwards, and purity is up to 97%.
In summary existing separation method, there is such as complicated for operation, low efficiency, energy consumption is high, at high cost etc. to ask
Topic.
Summary of the invention
To solve technical problem of the existing technology, the present invention provides a kind of using partially crystallizable and the side that crystallizes deeply
Formula is separated, simple, quick, efficient, to be economically separated ethylenediamine and n-ethylethylenediamine mixed solution method.
To achieve the above object, the technical scheme adopted by the invention is as follows a kind of separation ethylenediamine and n-ethylethylenediamine are mixed
The method for closing solution is operated in the way of crystallizing by partially crystallizable and deeply；
In terms of n-ethylethylenediamine quality, if the mass fraction of initial mixing solution less than 60%, first by initial mixing solution into
Row partially crystallizable crystallizes out higher melting-point ethylenediamine moiety, is then separated by solid-liquid separation, and isolated ethylenediamine is solid
Body, uncrystallized mixing liquid carries out deep crystallization treatment after then separating again, makes whole ethylenediamines and part N- ethyl second two
Amine crystallizes out, and is separated by solid-liquid separation again, and the solid mixture containing ethylenediamine and part n-ethylethylenediamine and not is obtained
The n-ethylethylenediamine liquid of crystallization after the filtering of n-ethylethylenediamine liquid, obtains n-ethylethylenediamine solid, then will be after separation
Solid mixture fusing after be added to recycled in initial mixing solution；
In terms of n-ethylethylenediamine quality, if the mass fraction of initial mixing solution is equal to or more than 60%, first by initial mixing
Solution carries out deep crystallization treatment, is then separated by solid-liquid separation, and isolated n-ethylethylenediamine liquid and contains ethylenediamine and portion
The solid mixture of n-ethylethylenediamine obtains n-ethylethylenediamine solid, then will consolidate after the filtering of n-ethylethylenediamine liquid
Body mixture is melted, then the liquid after fusing is carried out partially crystallizable processing, is separated by solid-liquid separation again, obtains ethylenediamine
Solid and liquid mixture containing part ethylenediamine and part n-ethylethylenediamine, then the liquid mixture after separation is added
The recycled into initial mixing solution.
Preferably, when carrying out partially crystallizable, by initial mixing solution in the environment of -22 DEG C~5 DEG C freezing and crystallizing
0.5h~for 24 hours；When carrying out deep crystallization, by initial mixing solution in the environment of -30 DEG C~0 DEG C freezing and crystallizing 2h~48h.
Preferably, when carrying out partially crystallizable, by initial mixing solution in the environment of -20 DEG C~-5 DEG C freezing and crystallizing
0.5h~5h；When carrying out deep crystallization, by initial mixing solution in the environment of -30 DEG C~-20 DEG C freezing and crystallizing 3h~15h.
Preferably, the purity and yield of separation product can be controlled by changing temperature and time.
Compared with prior art, the present invention has following technical effect that the present invention using partially crystallizable and the side crystallized deeply
Formula separates ethylenediamine and n-ethylethylenediamine mixed solution, in this way compared with prior art, operates simpler, effect
Rate is high, energy consumption is small, at low cost, and free of losses, pollution-free.Simultaneously separation product can be controlled by changing temperature and time
Purity and yield accomplish that purity is controllable with yield.In partially crystallizable operation, second two can be improved by increasing temperature and shortening time
The purity of amine, but the yield of ethylenediamine is also reduced simultaneously, in deep crystallization operation, reducing temperature and extension time can be improved
The purity of n-ethylethylenediamine, but the yield of n-ethylethylenediamine is also reduced simultaneously.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
In order to which technical problems, technical solutions and advantages to be solved are more clearly understood, tie below
Accompanying drawings and embodiments are closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
As shown in Figure 1, a kind of method for separating ethylenediamine and n-ethylethylenediamine mixed solution, according to partially crystallizable and depth
The mode of crystallization is operated；
In terms of n-ethylethylenediamine quality, if the mass fraction of initial mixing solution less than 60%, first by initial mixing solution into
Row partially crystallizable crystallizes out higher melting-point ethylenediamine moiety, is then separated by solid-liquid separation, and isolated ethylenediamine is solid
Body, uncrystallized mixing liquid carries out deep crystallization treatment after then separating again, makes whole ethylenediamines and part N- ethyl second two
Amine crystallizes out, and is separated by solid-liquid separation again, and the solid mixture containing ethylenediamine and part n-ethylethylenediamine and not is obtained
The n-ethylethylenediamine liquid of crystallization after the filtering of n-ethylethylenediamine liquid, obtains n-ethylethylenediamine solid, then will be after separation
Solid mixture fusing after be added to recycled in initial mixing solution；
In terms of n-ethylethylenediamine quality, if the mass fraction of initial mixing solution is equal to or more than 60%, first by initial mixing
Solution carries out deep crystallization treatment, is then separated by solid-liquid separation, and isolated n-ethylethylenediamine liquid and contains ethylenediamine and portion
The solid mixture of n-ethylethylenediamine obtains n-ethylethylenediamine solid, then will consolidate after the filtering of n-ethylethylenediamine liquid
Body mixture is melted, then the liquid after fusing is carried out partially crystallizable processing, is separated by solid-liquid separation again, obtains ethylenediamine
Solid and liquid mixture containing part ethylenediamine and part n-ethylethylenediamine, then the liquid mixture after separation is added
The recycled into initial mixing solution.
Wherein, when carrying out partially crystallizable, by initial mixing solution in the environment of -22 DEG C~5 DEG C freezing and crystallizing 0.5h
~for 24 hours；When carrying out deep crystallization, by initial mixing solution in the environment of -30 DEG C~0 DEG C freezing and crystallizing 2h~48h.
In order to preferably control the purity and yield of separation product, thus it is possible to vary temperature and time is carrying out partially crystallizable
When, by initial mixing solution in the environment of -20 DEG C~-5 DEG C freezing and crystallizing 0.5h~5h；It, will be initial when carrying out deep crystallization
Mixed solution freezing and crystallizing 3h~15h in the environment of -30 DEG C~-20 DEG C.
Analytic explanation is carried out with specific example below.
Embodiment one
7.69g ethylenediamine and 17.94gN- ethylethylenediamine are taken, mixing is 70%(with n-ethylethylenediamine to get mass fraction is arrived
Meter) mixed solution.Mixed solution is freezed into 12h in the environment of -28 DEG C, filters, obtains uncrystallized n-ethylethylenediamine
9.12g, yield 50.84%, purity 98.13%；In -15 after the crystal obtained after filtering is melted at room temperature simultaneously
1h is freezed in the environment of DEG C, is then filtered again, is obtained crystal ethylenediamine 5.44g, is melted at room temperature.The receipts of ethylenediamine
Rate is 70.74%, purity 98.11%；Finally uncrystallized liquid circulation is applied.
Embodiment two
18.45g ethylenediamine and 7.91gN- ethylethylenediamine are taken, mixing is 30%(with n-ethylethylenediamine to get mass fraction is arrived
Meter) mixed solution.Mixed solution is freezed into 1h in the environment of -15 DEG C, filters, obtains crystal ethylenediamine 12.08g,
Yield is 65.47%, purity 99.05%；The non-crystallized liquid obtained after filtering is freezed into 11h in the environment of -28 DEG C simultaneously,
Then it filters again, obtains uncrystallized n-ethylethylenediamine 5.52g, yield 54.76%, purity 98.57%；Finally will
Recycled after crystalline mixture fusing.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all wrap within the scope of the present invention within mind and principle.
Claims (4)
1. a kind of method for separating ethylenediamine and n-ethylethylenediamine mixed solution, it is characterised in that: according to partially crystallizable and depth
The mode of crystallization is operated；
In terms of n-ethylethylenediamine quality, if the mass fraction of initial mixing solution less than 60%, first by initial mixing solution into
Row partially crystallizable crystallizes out higher melting-point ethylenediamine moiety, is then separated by solid-liquid separation, and isolated ethylenediamine is solid
Body, uncrystallized mixing liquid carries out deep crystallization treatment after then separating again, makes whole ethylenediamines and part N- ethyl second two
Amine crystallizes out, and is separated by solid-liquid separation again, and the solid mixture containing ethylenediamine and part n-ethylethylenediamine and not is obtained
The n-ethylethylenediamine liquid of crystallization after the filtering of n-ethylethylenediamine liquid, obtains n-ethylethylenediamine solid, then will be after separation
Solid mixture fusing after be added to recycled in initial mixing solution；
In terms of n-ethylethylenediamine quality, if the mass fraction of initial mixing solution is equal to or more than 60%, first by initial mixing
Solution carries out deep crystallization treatment, is then separated by solid-liquid separation, and isolated n-ethylethylenediamine liquid and contains ethylenediamine and portion
The solid mixture of n-ethylethylenediamine obtains n-ethylethylenediamine solid, then will consolidate after the filtering of n-ethylethylenediamine liquid
Body mixture is melted, then the liquid after fusing is carried out partially crystallizable processing, is separated by solid-liquid separation again, obtains ethylenediamine
Solid and liquid mixture containing part ethylenediamine and part n-ethylethylenediamine, then the liquid mixture after separation is added
The recycled into initial mixing solution.
2. a kind of method for separating ethylenediamine and n-ethylethylenediamine mixed solution according to claim 1, feature exist
In: when carrying out partially crystallizable, by initial mixing solution in the environment of -22 DEG C~5 DEG C freezing and crystallizing 0.5h~for 24 hours；Into
When the deep crystallization of row, by initial mixing solution in the environment of -30 DEG C~0 DEG C freezing and crystallizing 2h~48h.
3. a kind of method for separating ethylenediamine and n-ethylethylenediamine mixed solution according to claim 2, feature exist
In: when carrying out partially crystallizable, by initial mixing solution in the environment of -20 DEG C~-5 DEG C freezing and crystallizing 0.5h~5h；Into
When the deep crystallization of row, by initial mixing solution in the environment of -30 DEG C~-20 DEG C freezing and crystallizing 3h~15h.
4. a kind of method for separating ethylenediamine and n-ethylethylenediamine mixed solution according to claim 1 to 3, feature
It is: the purity and yield of separation product can be controlled by changing temperature and time.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239134A (en) * | 2008-10-06 | 2011-11-09 | 陶氏环球技术有限责任公司 | Methods for making ethanolamine(s) and ethyleneamine(s) from ethylene oxide and ammonia, and related methods |
| CN102260175A (en) * | 2011-06-08 | 2011-11-30 | 浙江大学 | Method for synthesizing 2-aminoethyl(ethyl)amine |
| CN102816071A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Synthesis method of N-ethyl ethylene diamine |
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2018
- 2018-10-15 CN CN201811194713.0A patent/CN109134274B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239134A (en) * | 2008-10-06 | 2011-11-09 | 陶氏环球技术有限责任公司 | Methods for making ethanolamine(s) and ethyleneamine(s) from ethylene oxide and ammonia, and related methods |
| CN102260175A (en) * | 2011-06-08 | 2011-11-30 | 浙江大学 | Method for synthesizing 2-aminoethyl(ethyl)amine |
| CN102816071A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Synthesis method of N-ethyl ethylene diamine |
Non-Patent Citations (1)
| Title |
|---|
| 黄雪莉: "N-乙基乙二胺与乙二胺体系萃取精馏溶剂选择", 《化学工业与工程》 * |
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